Topography directed patterning

ABSTRACT

A pattern having exceptionally small features is formed on a partially fabricated integrated circuit during integrated circuit fabrication. The pattern comprises features formed by self-organizing material, such as diblock copolymers. The organization of the copolymers is directed by spacers which have been formed by a pitch multiplication process in which spacers are formed at the sides of sacrificial mandrels, which are later removed to leave spaced-apart, free-standing spacers. Diblock copolymers, composed of two immiscible block species, are deposited over and in the space between the spacers. The copolymers are made to self-organize, with each block species aggregating with other block species of the same type.

REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. patent application Ser. No.11/389,581, filed Mar. 23, 2006.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to integrated circuit fabrication and,more particularly, to printing techniques.

2. Description of the Related Art

As a consequence of many factors, including demand for increasedportability, computing power, memory capacity and energy efficiency,integrated circuits are continuously being made more dense. The sizes ofthe constituent features, e.g., electrical devices and interconnectlines, that form the integrated circuits are constantly being decreasedto facilitate this scaling.

The trend of decreasing feature size is evident, for example, in memorycircuits or devices such as dynamic random access memories (DRAMs),flash memory, static random access memories (SRAMs), ferroelectric (FE)memories, etc. To take one example, DRAM typically comprises millions ofidentical circuit elements, known as memory cells. In general, acapacitor-based memory cell, such as in conventional DRAM, typicallyincludes two electrical devices: a storage capacitor and an access fieldeffect transistor. Each memory cell is an addressable location that canstore one bit (binary digit) of data. A bit can be written to a cellthrough the transistor and can be read by sensing charge in thecapacitor. Some memory technologies employ elements that can act as botha storage device and a switch (e.g., dendritic memory employingsilver-doped chalcogenide glass) and some nonvolatile memories do notrequire switches for each cell (e.g., magnetoresistive RAM) orincorporate switches into the memory element (e.g., EEPROM). Bydecreasing the sizes of the electrical devices that constitute a memorycell and the sizes of the conducting lines that access the memory cells,the memory devices can be made smaller. Additionally, storage capacitiescan be increased by fitting more memory cells on a given area in thememory devices. The need for reductions in feature sizes, however, ismore generally applicable to integrated circuits, including generalpurpose and specialty processors.

The continual reduction in feature sizes places ever greater demands onthe techniques used to form the features. For example, photolithographyis commonly used to pattern these features. Typically, photolithographyinvolves passing light through a reticle and focusing the light onto aphotochemically-active photoresist material. Just as a slide has animage to be projected onto a screen, the reticle typically has a patternto be transferred to a substrate. By directing light or radiationthrough the reticle, the pattern in the reticle can be focused on thephotoresist. The light or radiation causes a chemical change in theilluminated parts of the photoresist, which allows those parts to beselectively retained, or removed, as desired, relative to parts whichwere in the shadows. Thus, the exposed and unexposed parts form apattern in the photoresist. It will be appreciated that this pattern canbe used as a mask to form various features of an integrated circuit,including conductive lines or parts of electrical devices.

Because lithography is typically accomplished by projecting light orradiation onto a surface, the ultimate resolution of a particularlithography technique depends upon factors such as optics and light orradiation wavelength. For example, the ability to focus well-definedpatterns onto resist depends upon the size of the features and on thewavelength of the radiation projected through the reticle. It will beappreciated that resolution decreases with increasing wavelength, due,among other things, to diffraction. Thus, shorter wavelength radiationis typically required to form well-resolved features, as the sizes ofthe features decrease. Consequently, to facilitate reductions in featuresizes, lower and lower wavelength systems have been proposed.

For example, 365 nm, 248 nm, 193 nm and 157 nm wavelength systems havebeen developed as features sizes have decreased. Additional reductionsin feature sizes, e.g., down to 20 nm features, may require even shorterwavelength systems. For example, X-ray based lithography, using X-rayradiation instead of light, has been proposed to form very smallfeatures, such as 20 nm features. Another proposed technology is extremeultraviolet (EUV) lithography, using, e.g., 13.7 nm radiation. X-ray andEUV lithography, however, are expected to be prohibitively expensive toimplement. In addition to cost, the techniques face various technicalobstacles. For example, for X-ray lithography, these obstacles includedifficulties in forming high quality reticles which are sufficientlyopaque to X-rays and difficulties in devising resists which aresufficiently sensitive to the X-rays. Moreover, rather than using opticsto focus radiation on the resist, some X-ray systems place the reticleclose to the resist, to directly expose the resist to X-rays passingthrough the reticle. This can cause complications in aligning thereticle with the resist and, in addition, places significant demands onthe flatness of both the reticle and the resist. In addition, X-raylithography can use reflective as opposed to refractive optics, whichcan require a complete redesign of optical elements and related systems.Similarly, other high resolution lithography techniques, including ionbeam and electron beam lithography, have their own technical andpractical obstacles, including high complexity and costs.

Accordingly, there is a continuing need for high resolution methods topattern small features on semiconductor substrates.

SUMMARY OF THE INVENTION

According to one aspect of the invention, a method is provided forforming a pattern over a semiconductor substrate. The method comprisesproviding a plurality of pitch multiplied features overlying thesemiconductor substrate. A self-organizing material is provided betweenthe pitch multiplied features. Segregation of chemical moieties formingthe self-organizing material is initiated.

According to another aspect of the invention, a method is provided forforming a mask pattern. The method comprises forming a plurality ofspacers by pitch multiplication. A film is deposited between thespacers. The film is annealed to form a repeating pattern of featureswithin the film.

According to yet another aspect of the invention, a method is providedfor semiconductor fabrication. The method comprises providing aplurality of lines having a pitch of about 200 nm or less. A patterncomprising block copolymers is formed between the plurality of lines.

According to another aspect of the invention, a method is provided formask formation. The method comprises providing a pattern of spacers overa semiconductor substrate. The method also comprises providing ahomogeneous mask material extending between the spacers. The maskmaterial is exposed to an etchant to form a pattern of voids in theexposed mask material.

According to yet another aspect of the invention, a method ofsemiconductor processing is provided. The method comprises forming afirst set of block domains over a semiconductor substrate. The first setof block copolymers includes a plurality of separated groups of blockdomains. The block domains are formed substantially by like blocks of ablock copolymer. A second set of block domains is subsequently formed inspaces between the separated groups of block domains.

According to another aspect of the invention, a partially fabricatedintegrated circuit is provided. The partially fabricated integratedcircuit comprises a plurality of copolymer guides overlying asemiconductor substrate, the guides having a pitch of about 200 nm orless. The partially fabricated integrated circuit also comprises blockcopolymers disposed between the plurality of copolymer guides.

BRIEF DESCRIPTION OF THE DRAWINGS

The invention will be better understood from the Detailed Description ofthe Preferred Embodiments and from the appended drawings, which aremeant to illustrate and not to limit the invention, and wherein:

FIG. 1 is a schematic cross-sectional side view of a partially formedintegrated circuit, in accordance with preferred embodiments of theinvention;

FIGS. 2 is a schematic cross-sectional side view of the partially formedintegrated circuit of FIG. 1 after forming features in a photoresistlayer, in accordance with preferred embodiments of the invention;

FIG. 3 is a schematic cross-sectional side view of the partially formedintegrated circuit of FIG. 2 after etching through a hard mask layer, inaccordance with preferred embodiments of the invention;

FIG. 4 is a schematic, cross-sectional side view of the partially formedintegrated circuit of FIG. 3 after removing the photoresistphotoresistand transferring a pattern from the hard mask layer to a temporarylayer, in accordance with preferred embodiments of the invention;

FIG. 5 is a schematic, cross-sectional side view of the partially formedintegrated circuit of FIG. 4 after a hard mask layer removal, inaccordance with preferred embodiments of the invention;

FIG. 6 is a schematic, cross-sectional side view of the partially formedintegrated circuit of FIG. 5 after depositing a layer of a spacermaterial, in accordance with preferred embodiments of the invention;

FIG. 7 is a schematic, cross-sectional side view of the partially formedintegrated circuit of FIG. 6 after a spacer etch, in accordance withpreferred embodiments of the invention;

FIG. 8 is a schematic, cross-sectional side view of the partially formedintegrated circuit of FIG. 7 after removing a remaining portion of thetemporary layer to leave a pattern of spacers, in accordance withpreferred embodiments of the invention;

FIG. 9 is a schematic, cross-sectional side view of the partially formedintegrated circuit of FIG. 8 after depositing a layer of a blockcopolymer solution, in accordance with preferred embodiments of theinvention;

FIG. 10 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 9 after self-organization of the blockcopolymers, in accordance with preferred embodiments of the invention;

FIGS. 11 and 12 are schematic, cross-sectional top views of thepartially formed integrated circuit of FIG. 10 showing two exemplarycopolymer arrangements resulting from the self-organization of the blockcopolymers, in accordance with preferred embodiments of the invention;

FIG. 13 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 12 after selectively removing one oftwo block copolymer blocks, in accordance with preferred embodiments ofthe invention;

FIG. 14 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 13 after transferring the patterndefined by the block copolymers into the underlying substrate, inaccordance with preferred embodiments of the invention;

FIGS. 15 is a schematic, cross-sectional side view of a partially formedintegrated circuit after transferring a pattern defined by the blockcopolymers into a hard mask layer and then into an underlying substrate,in accordance with preferred embodiments of the invention;

FIG. 16 is a schematic, cross-sectional side view of a partially formedintegrated circuit after forming spacers on sidewalls of mandrels, inaccordance with other preferred embodiments of the invention;

FIG. 17 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 16 after depositing a layer of a blockcopolymer solution, in accordance with preferred embodiments of theinvention;

FIG. 18 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 17 after self-organization of theblock copolymers, in accordance with preferred embodiments of theinvention;

FIG. 19 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 18 after selectively removing one oftwo copolymer blocks, transferring the pattern formed by the remainingcopolymer blocks into an underlying hardmask layer and removing theremaining copolymer blocks, in accordance with preferred embodiments ofthe invention;

FIG. 20 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 19 after depositing a layer of fillermaterial to fill in spaces between the spacers and planarizing to exposethe mandrels, in accordance with preferred embodiments of the invention;

FIG. 21 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 20 after removing the mandrels, inaccordance with preferred embodiments of the invention;

FIG. 22 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 21 after depositing a second layer ofa block copolymer solution, in accordance with preferred embodiments ofthe invention;

FIG. 23 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 22 after self-organization of blockcopolymers, in accordance with preferred embodiments of the invention;

FIG. 24 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 23 after selectively removing one oftwo copolymer block species relative to the other block species andrelative to the filler material, in accordance with preferredembodiments of the invention;

FIG. 25 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 24 after transferring the patternedformed by the remaining blocks into the underlying hardmask layer andremoving the filler material, in accordance with preferred embodimentsof the invention; and

FIG. 26 is a schematic, cross-sectional side view of the partiallyformed integrated circuit of FIG. 25 after transferring a patterndefined by the copolymer blocks into an underlying substrate, inaccordance with preferred embodiments of the invention.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The ability of block copolymers to self-organize can be used to formmask patterns. Block copolymers are formed of two or more chemicallydistinct blocks. For example, each block can be formed of a differentmonomer. The blocks are preferably immiscible or thermodynamicallyincompatible, e.g., one block can be polar and the other can benon-polar. Due to thermodynamic effects, the copolymers willself-organize in solution to minimize the energy of the system as awhole; typically, this causes copolymers to move relative to oneanother, e.g., so that like blocks aggregate together, thereby formingalternating regions containing each block type or species. For example,if the copolymers are formed of polar and non-polar blocks, the blockswill segregate so that non-polar blocks aggregate with other non-polarblocks and polar blocks aggregate with other polar blocks. It will beappreciated that the block copolymers may be described as aself-organizing material since the blocks can move to form a patternwithout application of an external force to direct the movement ofindividual molecules, although heat may be applied to increase the rateof movement as noted below.

In addition to interactions between the block species, theself-organization of block copolymers can be influenced by topographicalfeatures, such as steps on the surface on which the block copolymers aredeposited. For example, a diblock copolymer, a copolymer formed of twodifferent block species, can form alternating regions which are eachformed of a substantially different block species. When theself-organization occurs in the area between the walls of a step, thesteps can interact with the blocks such that each of the alternatingregions formed by the blocks can be made to extend parallel to thewalls.

Such self-organization can be useful in forming masks for patterningfeatures during semiconductor fabrication processes. For example, one ofthe alternating regions can be removed, thereby leaving the otherregions to function as a mask. The mask can be used to pattern featuressuch as electrical devices in an underlying semiconductor substrate.

It will be appreciated that the size of the alternating regions isrelated to the size of the block copolymers and can be on the order ofnanometers or tens of nanometers. Various lithography methods, such asX-ray, EUV, ion beam and electron beam lithography are possiblecandidates for forming the closely-spaced step features. However,application of these methods, as noted above, has various technical andpractical obstacles which can make their use impractical andprohibitively expensive.

In preferred embodiments of the invention, rather than defining thesteps in a single lithography step, relatively large features are firstdefined and smaller step features are then derived from the relativelylarge features. Block copolymers are then applied around the steps andallowed to self-organize in the space between the step, or guide,features. Some of the blocks are subsequently selectively removed. Theremaining block species can be used as a mask for subsequent patterningof underlining materials during, e.g., the fabrication of integratedcircuits.

Preferably, pitch multiplication is used to form the small stepfeatures. For example, a relatively large feature can be patterned byconventional photolithography to form a pattern of temporaryplaceholders, or mandrels. Spacers are formed on the sides of themandrels and the mandrels are then removed, leaving a pattern offree-standing spacers which can function as guides for directing theself-organization of block copolymers.

Pitch multiplication advantageously allows the formation of small,closely-spaced step features which might otherwise be formed usingnewer, relatively complex and expensive lithography techniques.Advantageously, conventional, proven and relatively inexpensivelithography techniques can be utilized, thereby reducing costs andincreasing process reliability. Moreover, the self-organizing behaviorof block copolymers allows the reliable formation of very smallfeatures, thereby facilitating the formation of a mask with a very smallfeature size. For example, features having a critical dimension of about50 nm or less, more preferably, about 30 nm or less and, more preferablyabout 20 nm or less can be formed.

Reference will now be made to the Figures, wherein like numerals referto like parts throughout. It will be appreciated that the Figures arenot necessarily drawn to scale.

In a first phase of methods according to the preferred embodiments, aplurality of spacers is formed over a substrate by pitch multiplication.Suitable pitch multiplication techniques are described in U.S. Pat. No.5,328,810, issued to Lowrey et al., and U.S. patent application Ser. No.11/214,544, by Tran et al., filed Aug. 29, 2005. The entire disclosuresof these references are incorporated by reference herein. It will beappreciated that the preferred embodiments can be applied to form masksused in the fabrication of various integrated circuits. These integratedcircuits can include, e.g., memory chips or computer processors.

With reference to FIG. 1, a cross-sectional side view of a partiallyformed integrated circuit 100 is illustrated. Various layers 120-140 arepreferably provided above a substrate 110 to facilitate pitchmultiplication. The materials for the layers 120-140 overlying thesubstrate 110 are preferably chosen based upon consideration of theinteraction of the layers with block copolymer materials to be used andof the chemistry and process conditions for the various pattern formingand pattern transferring steps discussed herein. Because patterns inupper layers are preferably transferred to lower layers during pitchmultiplication, lower masking layers 130, 140 between a selectivelydefinable layer 120 and the substrate 110 are preferably chosen so thatthey can be selectively etched relative to other exposed materials. Itwill be appreciated that a material is considered selectively, orpreferentially, etched when the etch rate for that material is at leastabout 2-3 times greater, preferably at least about 10 times greater,more preferably at least about 20 times greater and, most preferably, atleast about 40 times greater than that for surrounding materials.Because an objective for the layers 120-140 is to allow well-definedpatterns to be formed above the substrate 110, it will be appreciatedthat one or more of the layers 120-140 can be omitted or substituted, oradditional layers can be added, if suitable other materials, chemistriesand/or process conditions are used.

It will be appreciated that the “substrate” to which patterns aretransferred can include a layer of a single material, a plurality oflayers of different materials, a layer or layers having regions ofdifferent materials or structures in them, etc. These materials caninclude semiconductors, insulators, conductors, or combinations thereof.For example, the substrate can comprise doped polysilicon, an electricaldevice active area, a silicide, or a metal layer, such as a tungsten,aluminum or copper layer, or combinations thereof. In some embodiments,the mask features discussed below can directly correspond to the desiredplacement of conductive features, such as interconnects, in thesubstrate. In other embodiments, the substrate can be an insulator andthe location of mask features can correspond to the desired location ofinsulation between conductive features, such as in damascenemetallization.

With continued reference to FIG. 1, the selectively definable layer 120overlies a hard mask, or etch stop, layer 130, which overlies atemporary layer 140, which overlies the substrate 110. The selectivelydefinable layer 120 is preferably photodefinable, e.g., formed of aphotoresist, including any photoresist known in the art. For example,the photoresist can be any photoresist compatible with 157 nm, 193 nm,248 nm or 365 nm wavelength systems, 193 nm wavelength immersionsystems. Examples of preferred photoresist materials include argonfluoride (ArF) sensitive photoresist, i.e., photoresist suitable for usewith an ArF light source, and krypton fluoride (KrF) sensitivephotoresist, i.e., photoresist suitable for use with a KrF light source.ArF photoresists are preferably used with photolithography systemsutilizing relatively short wavelength light, e.g., 193 nm. KrFphotoresists are preferably used with longer wavelength photolithographysystems, such as 248 nm systems. In addition, while pitch multiplicationcan obviate the need to define extremely small features with expensive,relatively new direct formation techniques such as extreme ultravioletsystems (including 13.7 nm wavelength systems) or electron beamlithographic systems, such systems can also be used, if desired. Inaddition, maskless lithography, or maskless photolithography, can beused to define the selectively definable layer 120. In otherembodiments, the layer 120 and any subsequent resist layers can beformed of a resist that can be patterned by nano-imprint lithography,e.g., by using a mold or mechanical force to form a pattern in theresist.

The material for the hard mask layer 130 preferably comprises aninorganic material. Exemplary materials include silicon oxide (SiO₂),silicon or a dielectric anti-reflective coating (DARC), such as asilicon-rich silicon oxynitride. Preferably, the hard mask layer 130 isa dielectric anti-reflective coating (DARC). Using DARCs for the hardmask layer 130 can be particularly advantageous for forming patternshaving pitches near the resolution limits of a photolithographictechnique. The DARCs can enhance resolution by minimizing lightreflections, thus increasing the precision with which photolithographycan define the edges of a pattern.

The temporary layer 140 is preferably formed of amorphous carbon, whichoffers very high etch selectivity relative to the preferred hard maskmaterials. More preferably, the amorphous carbon is a form of amorphouscarbon that is highly transparent to light and that offers furtherimprovements for photo alignment by being transparent to the wavelengthsof light used for such alignment. Techniques for forming suchtransparent carbon can be found in A. Helmbold, D. Meissner, Thin SolidFilms, 283 (1996) 196-203. The entire disclosure of this reference isincorporated herein by reference.

With reference to FIG. 2, the photodefinable layer 120 is exposed toradiation through a reticle and then developed to leave a patterncomprising features 122 which are formed of photodefinable material. Itwill be appreciated that the pitch of the resulting features 122, e.g.,lines, is equal to the sum of the width of a line 122 and the width of aneighboring space 124. If desired, the dimensions of the line 122 can beadjusted by using, e.g., an isotropic etch to decrease both the heightand the width of the line 122. The pitch of the features 122 can be,e.g., about 200 nm or about 120 nm.

With reference to FIG. 3, the pattern in the photodefinable layer 120 istransferred to the hard mask layer 130 thereby forming features 132 inthe hard mask layer 130. In particular, FIG. 3 shows the features 122and 132 in isolation. The pattern transfer is preferably accomplishedusing an anisotropic etch, such as an etch using a fluorocarbon plasma,although a wet (isotropic) etch may also be suitable if the hard masklayer 130 is sufficiently thin. Preferred fluorocarbon plasma etchchemistries include CFH₃, CF₂H₂, CF₃H and CF₄/HBr. Resist forming thephotodefinable layer 120 can optionally be removed, e.g., by plasmaashing. In the illustrated embodiment, the resist removal can be delayedand advantageously is efficiently performed in a single step withetching of the temporary layer 140.

With reference to FIG. 4, the pattern in the photodefinable layer 120and the hard mask layer 130 is transferred to the temporary layer 140 toallow for deposition of a layer 150 of spacer material (FIG. 6). It hasbeen found that the temperatures used for spacer material deposition aretypically too high for photoresist to withstand. Thus, the pattern ispreferably transferred from the features 122 in the photodefinable layer120 (FIG. 3) to the temporary layer 140, which is formed of a materialthat can withstand the process conditions for spacer material depositionand etch, discussed below. In addition to having higher heat resistancethan photoresist, the material forming the temporary layer 140 ispreferably selected such that it can be selectively removed relative tothe material for the spacers 152 (FIG. 7) to be formed and anyunderlying material, e.g., the substrate 110. As noted above, the layer140 is preferably formed of amorphous carbon and, more preferably,transparent carbon.

The pattern of features 122 in the modified photodefinable layer 120 ispreferably transferred to the temporary layer 140 using an O₂-containingplasma, e.g., a plasma containing SO₂, O₂ and Ar. Other suitable etchchemistries include a Cl₂/O₂/SiCl₄ or SiCl₄/O₂/N₂ or HBr/O₂/N₂/SiCl₄containing plasma. Advantageously, the SO₂-containing plasma is used asit can etch carbon of the preferred temporary layer 140 at a rategreater than 20 times and, more preferably, greater than 40 times therate that the hard mask layer 130 is etched. A suitable SO₂-containingplasma is described in U.S. patent application Ser. No. 10/931,772 toAbatchev et al., filed Aug. 31, 2004, the entire disclosure of which isincorporate herein by reference. It will be appreciated that theSO₂-containing plasma can simultaneously etch the temporary layer 140and also remove the features 122 formed from the photodefinable layer120. The resulting lines 142 in the temporary layer 140 constitute theplaceholders or mandrels along which a pattern of spacers 152 (FIG. 7)will be formed.

With reference to FIG. 5, the material 132 from the hard mask layer 130(FIG. 4) can be removed to facilitate later spacer formation by leavingthe temporary layer 140 exposed for subsequent etching (FIG. 8). Thepreferred hard mask layer 130 can be removed using a buffered oxide etch(BOE), which is a wet etch comprising HF and NH₄F.

Next, as shown in FIG. 6, a layer 150 of spacer material is preferablyblanket deposited conformally over exposed surfaces, including the hardmask layer 130 (if remaining) and the top and sidewalls of the mandrels142. The spacer material can be any material that can act as a mask fortransferring a pattern to the underlying substrate 110 and allows foretch selectivity relative to one or more block species of a blockcopolymer, as discussed below. The spacer material preferably: 1) can bedeposited with good step coverage; and 2) can be deposited at atemperature compatible with the temporary layer 140. Preferred materialsinclude silicon, silicon oxides and silicon nitrides. In the illustratedembodiment, the spacer material is silicon oxide, which providesparticular advantages in combination with other selected materials ofthe masking stack.

Preferred methods for spacer material deposition include chemical vapordeposition, e.g., using O₃ and TEOS to form silicon oxide, and atomiclayer deposition, e.g., using a silicon precursor with an oxygen ornitrogen precursor to form silicon oxides or nitrides, respectively. Thethickness of the layer 150 is preferably determined based upon thedesired width of the spacers 152 (FIG. 8). Preferably, the step coverageis about 80% or greater and, more preferably, about 90% or greater.Advantageously, atomic layer deposition allows for a high degree ofcontrol over the thickness of the deposited layer 150. This control canbe especially beneficial when forming guides for block copolymers, sincethe self-organization of the block copolymers is influenced by thethickness of the deposited block copolymer material and since the heightof the spacers 152 is preferably sufficiently close to the thickness ofthe block copolymer material (to be deposited) to allow some blockcopolymer material to overlie the spacers 152 while still beingcontinuous with copolymer material between the spacers 152.Advantageously, as noted below, having copolymer material overlying thespacers 152 can provide a reservoir of copolymer material which canguard against the depletion of copolymers during copolymerself-organization.

With reference to FIG. 7, the silicon oxide spacer layer 150 is thensubjected to an anisotropic etch to remove spacer material fromhorizontal surfaces 154 of the partially formed integrated circuit 100.Such an etch, also known as a spacer etch, can be performed using afluorocarbon plasma, e.g., containing CF₄/CHF₃, C₄F₈/CH₂F₂ or CHF₃/Arplasma.

With reference to FIG. 8, the mandrels or temporary placeholders 142(FIG. 7) are next removed to leave freestanding spacers 152. Themandrels 142 are selectively removed using an organic strip process.Preferred etch chemistries include a oxygen-containing plasma etch, suchas an etch using SO₂.

As noted above, the height of the spacers 152 can influence theorganization of block copolymers, as noted below. As a result, thespacers 152 can optionally be trimmed, e.g., using an anisotropic etch.In other embodiments, the height of the mandrels 142 (FIG. 6) and/or thethickness of the temporary layer 140 (FIG. 1) can be selected so as toform spacers 152 of the desired height.

With continued reference to FIG. 8, pitch multiplication has thus beenaccomplished. In the illustrated embodiment, the pitch of the spacers152 is roughly half that of the photoresist lines 122 and spaces 124(FIG. 2) originally formed by photolithography. For example, where thephotoresist lines 122 had a pitch of about 400 nm, spacers 152 having apitch of about 200 nm or less can be formed. In some embodiments wherethe photoresist lines 122 had a pitch of about 200 nm, spacers 152having a pitch of about 100 nm or less can be formed.

Block copolymers are next applied and block copolymer self-organizationis facilitated to form a mask pattern over the substrate 110. A suitablemethod for forming self-organized block copolymer patterns is disclosedin Block, IEE Transactions in Nanotechnology, Vol. 3, No. 3, September2004. The entire disclosure of that reference is incorporated byreference herein.

With reference to FIG. 9, a film 160 of block copolymer material isdeposited between and over the spacers 152. The copolymer comprisesblocks of polymer material which can be selectively etched relative toone another and can self-organize in a desired and predictable manner,e.g., the blocks are preferably immiscible and will segregate underappropriate conditions to form domains predominantly containing a singleblock species. In the exemplary illustrated embodiment, the copolymer isa diblock copolymer, comprising, e.g., polystyrene (PS) andpoly-methylmethacrylate (PMMA) in a 70:30 PS:PMMA ratio with a totalmolecular weight of 64 kg/mol. The diblock copolymer can be provideddissolved in a solvent, e.g., toluene. Preferably, the copolymers aresubstantially all the same size and composition, to increase thepredictability and regularity of the patterns formed by theself-organization of the copolymers. It will be appreciated that thetotal size of each diblock copolymer and the ratio of the constituentblocks and monomers are preferably chosen to facilitateself-organization and to form organized block domains having desireddimensions. The block copolymers have an intrinsic polymer length scale,the average end-to-end length of the copolymer in film, including anycoiling or kinking, which governs the size of the block domains. Longercopolymers may be used to form larger domains and shorter copolymers maybe used to form smaller domains. The block copolymer can be deposited byvarious methods, including, e.g., spin-on coating, spin casting, brushcoating or vapor deposition.

The thickness of the copolymer film 160 can be chosen based upon thedesired pattern to be formed by the copolymers. It will be appreciatedthat, up to a particular thickness related to the polymer length scaleand the environment in which the polymers are disposed, e.g., thedistance between and the height of the spacers 152, the copolymers willtypically orient to form alternating, substantially lamellar domainsthat form parallel lines, as viewed in a top-down view (FIG. 11). Suchlamellae can be used to pattern, e.g., interconnects, or the lateralextension of the lamellae can be limited to form isolated features,e.g., transistor gates. Above a particular thickness related to thepolymer length scale and the environment in which the polymers aredisposed, the copolymers will typically orient to formvertically-extending pillars, such as cylinders, or spheres (FIG. 12).The cylinders can advantageously be used to pattern isolated features,e.g., vias or transistor gates. Thus, the pattern to be formed canadvantageously be selected by appropriate selection of copolymer filmthickness. Alternatively, other variables, such as copolymer compositionor process conditions can be modified to facilitate the formation ofvertically extending pillars or horizontally extending lamellae for agiven thickness through appropriate selection of interfacialinteractions between the blocks of the copolymer as well as thesubstrate surfaces. The thickness of the film 160 can be greater than,equal to or less than the height of the spacers 152. As noted below, athickness which is greater than the height of the spacers can haveadvantages for providing a copolymer reservoir. In other embodiments, athickness which is equal to or, more preferably, less than the height ofthe spacers can be advantageous by forming isolated islands ofcopolymers between the spacers 152, thereby preventing cross-diffusionof copolymers between the islands.

For forming lamellae, the copolymer film thickness is preferably lessthan about the length scale of the copolymer. For example, in theillustrated embodiment, the copolymer length scale is about 35 nm andthe thickness of the films is preferably about 35 nm or less, morepreferably, about 30 nm or less and, most preferably, about 25 nm orless. In one embodiment, the thickness is about 20 nm.

With reference to FIG. 10, the block copolymers in the copolymer film160 are allowed to self-organize. The self-organization can befacilitated and accelerated by annealing the partially-fabricatedintegrated circuit 100. The temperature of the anneal is preferablychosen to be sufficiently low to prevent adversely affecting the blockcopolymers or the partially-fabricated integrated circuit 100. In theillustrated embodiment, the anneal is preferably performed at atemperature of less than about 250° C., more preferably, less than about200° C. and, most preferably, about 180° C. Advantageously, the annealcan also cause cross-linking of the copolymers, thereby stabilizing thecopolymers for later etching and pattern transfer steps.

The pattern of lamellae resulting after the anneal is shown in FIG. 10.Domains 162 of one block species, e.g., PS, and domains 164 of the otherblock species, e.g., PMMA, alternate between the spacers 152. It will beappreciated that the sizes of the block domains are determined by thesizes of the block species forming them.

With reference to FIG. 11, a top-down view of the partially fabricatedintegrated circuit of FIG. 10 is shown. The PS domains 162 can be seenalternating with the PMMA domains 164. Both domains 162 and 164 extendalong the length of the spacers 152.

With reference to FIG. 12, in other embodiments, the thickness of thecopolymer film 160 (FIG. 9) is chosen so as to form vertically extendingcylinders (or other isolated pillar shapes, including pillars havingrectangular or cubic horizontal cross-sectional areas) comprising PS andPMMA. The resulting arrangement, from a top-down view, has regions 162 aof PS surrounded by regions 164 a of PMMA. Such an arrangement can beuseful for forming, e.g., contact vias. In addition, the pillars canadvantageously be applied in some arrangements for patterning arrays offeatures, particularly dense arrays of features, such as capacitors formemory applications, including DRAM. In such arrangements, the pillarscan have a rectangular or cubic horizontal cross-sectional area, whichcan have advantages by providing a higher surface area structure.

With reference to FIG. 13, the PMMA domains 164 of FIGS. 10 and 11 areselectively removed, leaving behind the spacers 152 and the PS domains162. The removal can be accomplished by performing a wet etch, e.g.,using acetic acid as an etchant. In other embodiments, a dry oranisotropic etch may be appropriate where one of the domains can beetched at a faster rate than the other. It will be appreciated that thedimensions of the resulting features can vary, depending on the size ofthe copolymer used and process conditions. In some embodiments, theresulting pattern can advantageously comprise PS domains having acritical dimension of about 20 nm separated by spaces of about 20 nm. Itwill be appreciated that in other embodiments, the PS domains 162 and/orthe spacers 152 can be removed instead, thereby leaving the PMMA domain164, with or without the spacers 152.

With reference to FIG. 14, the spacers 152 and domains 162 can be usedas a mask for processing of the underlying substrate 110. For example,the substrate 110 can be etched through the mask using, e.g., ananisotropic etch that selectively etches the substrate relative to boththe spacers 152 and domains 162 to transfer the pattern in the mask tothe substrate 110. In one example, where the spacers 152 are formed ofsilicon oxide and the substrate 110 is formed of silicon, the substrate110 can be selectively etched relative to the spacers 152 and to theblock domains 162 using a fluorine-based dry etch chemistry, e.g., suchas that used to selectively remove silicon layers relative tophotoresist. It will be appreciated that where the substrate 110comprises layers of different materials, a succession of differentchemistries, preferably dry-etch chemistries, can be used tosuccessively etch through these different layers, if a single chemistryis not sufficient to etch all the different materials. It will also beappreciated that, depending upon the chemistry or chemistries used, thespacers 152 and the domains 162 may be etched. Consequently, withreference to FIG. 15, in some embodiments, the pattern formed by thespacers 152 and domains 162 can be transferred to an underlying hardmask layer 170, having good etch selectivity relative to substratematerials, before etching the substrate 110.

While the invention is not bound by theory, it will be appreciated thatthe different block species can self-aggregate due to thermodynamicconsiderations in a process similar to the phase separation ofmaterials. The self-organization is guided by the spacers 152 (FIG. 9),which encourage the constituent blocks of the block copolymers to orientthemselves along the length of the spacers 152. It will be appreciatedthat the self-organization can result in a more efficient packing of thecopolymer species, such that copolymers available for theself-organization can be depleted if the copolymer film 160 extends overtoo large of an expanse, causing an area in the middle of the expanse tobe formed without organized copolymers. In some embodiments, it willalso be appreciated that the copolymer film 160 is preferably sufficientthick to extend above the spacers 152 to provide a reservoir ofcopolymers for the self-organization which occurs between the spacers152. Moreover, the distance between the spacers 152 is preferably chosento be sufficiently small to minimize the depletion effect that can occurover large expanses.

In other embodiments, the reservoir region above the spacers 152 can beenlarged beyond the spacers 152. Such an enlargement can have advantagesfor forming well-defined block domains between relatively widelyseparated spacers 152.

With reference to FIG. 16, the steps shown with reference FIGS. 1-6 canbe used to form spacers 152 on the sides of mandrels 142, resulting in apartially fabricated integrated 102. The spacers 152 and mandrels 142overly a hardmask layer 112, which overlies a substrate 110.

With reference to FIG. 17, a first layer 162 of block copolymer materialis deposited between the spacers 152 and also over the spacers 152 andthe mandrels 142. Advantageously, the mandrels 142 provide a relativelylarge surface area which allows the formation of a large reservoir 164of block copolymer material. The block copolymer material can be similarto the block copolymer material discussed above, comprising, e.g., PSand PMMA, and can have a selected thickness as noted above.

With reference to FIG. 18, the copolymers are allowed to self-organize,which can be accelerated by, e.g., annealing the partially fabricatedintegrated circuit 102. After the self-organization, a first set ofalternating domains 162 of one block species, e.g., PS, and domains 164of the other block species, e.g., PMMA, are formed in the open spacebetween the spacers 152.

With reference to FIG. 19, some of the block domains, e.g., the blockdomains 164, are selectively removed, the pattern defined by theremaining domains 162 is transferred to the underlying hardmask layer112 (e.g., by an anisotropic etch selective for the hardmask layer 112)and the domains 162 are also removed, leaving behind a pattern offeatures 114 in the hardmask layer 112. It will be appreciated that, ina top down view, the features 114 can be lines or cylinders, as shown inFIGS. 11 and 12.

With reference to FIG. 20, a fill layer 116 is deposited around and overthe features 114 to fill in the spaces between the spacers 152. The filllayer 116 is preferably formed of a planarizing material that can bespun on and that can fill the gaps between the features 114. Examples ofplanarizing materials for the fill layer 116 include photoresist or aspin on dielectric (SOD). The fill layer 116 can be planarized, e.g., bychemical mechanical polishing, or etched back to ensure that themandrels 142 are exposed, as illustrated.

With reference to FIG. 21, the mandrels 142 are selectively removed.With reference to FIG. 22, a second layer 180 of copolymer material isdeposited. The copolymer material preferably occupies the open spacebetween the spacers 152 and also overlies the remaining parts of thelayer 116, forming a reservoir 184 of copolymer material over thoseareas. It will be appreciated that the copolymer material can be thesame as that deposited to form the layer 162 (FIG. 17), although thematerial for the layers 180 and 162 can be different in someembodiments.

With reference to FIG. 23, copolymers in the copolymer layer 180self-organize, e.g., during an anneal, to form a second set ofalternating block domains 186 and 188. With reference to FIG. 24, one ofthe domains, e.g., the domains 186, are selectively removed, leavingbehind the domains 188.

With reference to FIG. 25, the pattern defined by the domains 188 istransferred to the underlying hardmask layer 112 (e.g., by ananisotropic etch selective for the hardmask layer 112) and the remainderof the fill layer 116 is removed. Depending upon process parameters andthe interactions of the blocks of the block copolymer material with eachother and with exposed surfaces, the features 114 and 188 can appear, ina top down view, as lines or isolated cylinders (FIGS. 11 and 12,respectively).

Advantageously, in other embodiments, because the features 114 and 188have been formed separately, those features can be made to organize intodifferent patterns by establishing the appropriate conditions of thedesired type of pattern. For example, the features 114 can form apattern of cylinders, while the features 188 can form a pattern oflines. This can be accomplished, e.g., by using different copolymercompositions to form each of the features 114 or 188, or by increasingthe tendency of the blocks to form lines by decreasing the height of thespacers 152, e.g., during a CMP or etch back process to expose themandrels 142 (FIG. 20). In addition, the size and/or spacing betweenfeatures 114 or 188, whether lines and/or vertical pillars, canadvantageously be varied by, e.g., appropriate selection of chemicalspecies and process conditions.

With reference to FIG. 26, the spacers 152 and the domains 114 and 152can be used as a mask for processing of the underlying substrate 110. Asillustrated, the pattern defined by the domains 114 and 152 can betransferred to the substrate 110 using, e.g., an anisotropic etchselective for the material forming the substrate 110. As noted above, insome embodiments, the pattern can first be transferred to one or moreintervening hardmask layers (not shown) before being transferred to thesubstrate 110.

It will be appreciated that various modifications of the preferredembodiments are possible. For example, while discussed in the context ofdiblock copolymers, the copolymers can be formed of two or more blockspecies. Moreover, while the block species of the illustrated embodimentare each formed of a different monomer, the block species can sharemonomer(s). For example, the block species can be formed of differentsets of monomers, some of which are the same, or can be formed of thesame monomer, but in a different distribution in each block. Preferably,the different sets of monomers form blocks having different propertieswhich can drive the self-organization of the copolymers.

In some embodiments, the hardmask and/or temporary layer overlying thesubstrate can be omitted. For example, the photodefinable material canbe formed of or replaced by a material which has compatible with thetemperatures and other conditions for spacer formation. In theillustrated embodiment, however, the hardmask and spacer layers arepreferred for allowing high quality pattern transfers and for forminghigh quality spacers.

Also, while “processing” through a mask layer preferably involvesetching an underlying layer, processing through the mask layers caninvolve subjecting layers underlying the mask layers to anysemiconductor fabrication process. For example, processing can involveion implantation, diffusion doping, depositing, or wet etching, etc.through the mask layers and onto underlying layers. In addition, themask layers can be used as a stop or barrier for chemical mechanicalpolishing (CMP) or CMP can be performed on any of the layers to allowfor both planarization and etching of the underlying layers, asdiscussed in U.S. Provisional Patent Application No. 60/666,031, filedMar. 28, 2005, the entire disclosure of which is incorporated byreference herein.

In addition, while illustrated applied to an exemplary sequence forfabricating integrated circuits, it will be appreciated that thepreferred embodiments can be applied in various other applications whenthe formation of patterns with very small features is desired. Forexample, the preferred embodiments can be applied to form gratings, diskdrives, storage media or templates or masks for other lithographytechniques, including X-ray or imprint lithography.

Accordingly, it will be appreciated by those skilled in the art thatthese and various other omissions, additions and modifications may bemade to the methods and structures described above without departingfrom the scope of the invention. All such modifications and changes areintended to fall within the scope of the invention, as defined by theappended claims.

1. A method of semiconductor processing, comprising: forming a first setof block domains over a semiconductor substrate, the first setcomprising a plurality of separated groups of block domains, each groupcomprising a plurality of block domains, the block domains formedsubstantially by like blocks of a block copolymer; and subsequentlyforming a second set of block domains in spaces between the separatedgroups of block domains.
 2. The method of claim 1, wherein forming thefirst set comprises: providing a plurality of separated guides forcopolymer alignment over the semiconductor substrate; depositing a firstlayer of block copolymers into open volumes between the guides; andforming the first set of block domains from the block copolymers in theopen volumes.
 3. The method of claim 2, wherein forming the blockdomains comprise annealing the block copolymers.
 4. The method of claim2, further comprising transferring a pattern formed by the first set ofblock domains into an underlying hardmask layer to define mask featuresin the hardmask layer before subsequently forming the second set ofblock domains.
 5. The method of claim 4, wherein transferring thepattern formed by the first set of block domains into the underlyinghardmask layer comprises: selectively removing some of the block domainsof the first set of block domains to form openings defined by theremaining block domains of the first set of block domains; and etchingthe underlying hardmask layer through the openings.
 6. The method ofclaim 4, further comprising depositing a filler material around and overthe mask features in the hardmask layer.
 7. The method of claim 6,further comprising partially removing the filler material to expose topsof the separated guides.
 8. The method of claim 7, wherein partiallyremoving the filler material comprises performing a chemical mechanicalpolishing process.
 9. The method of claim 7, wherein partially removingthe filler material comprises performing an etch back process.
 10. Themethod of claim 6, further comprising exposing the guides to etchant toopen areas between edges of the guides to form the spaces between theseparated groups of block domains.
 11. The method of claim 10, furthercomprising depositing a second layer of block copolymers in the spacesbefore forming the second set of block domains in the spaces.
 12. Themethod of claim 11, wherein the first and second layer of blockcopolymers comprises a same block copolymer.
 13. The method of claim 12,wherein the block copolymer is formed of blocks of polystyrene andpoly-methylmethacrylate.
 14. The method of claim 11, wherein the secondlayer of block copolymers is disposed on a vertical level above thehardmask layer.
 15. The method of claim 11, wherein the guides comprisespacers disposed on sidewalls of the each of a plurality of separatedsacrificial mandrels.
 16. The method of claim 11, wherein exposing theguides to etchant comprises selectively removing the mandrels.
 17. Themethod of claim 11, further comprising transferring a pattern formed bythe second set of block domains into an underlying hardmask layer. 18.The method of claim 11, further comprising transferring a pattern formedby the first and the second set of block domains into the underlyingsubstrate.
 19. The method of claim 11, wherein the first set of blockdomains form features chosen from the group consisting of verticallamellae, isolated pillars or vertical cylinders.
 20. The method ofclaim 19, wherein the second set of block domains form features chosenfrom the group consisting of vertical lamellae, isolated pillars orvertical cylinders.
 21. The method of claim 20, wherein the first andthe second set of block domains form a same type of feature.
 22. Apartially fabricated integrated circuit, comprising: a plurality ofguides for copolymer alignment overlying a semiconductor substrate, theguides having a pitch of about 200 nm or less; and block copolymersdisposed between the plurality of copolymer guides.
 23. The partiallyfabricated integrated circuit of claim 22, wherein the guides forcopolymer alignment are pitch multiplied spacers.
 24. The partiallyfabricated integrated circuit of claim 22, wherein the pitch is about100 nm or less.
 25. The partially fabricated integrated circuit of claim22, wherein the block copolymers are formed of two block types.
 26. Thepartially fabricated integrated circuit of claim 25, wherein the blocksdefine lines having a critical dimension of about 50 nm or less.
 27. Thepartially fabricated integrated circuit of claim 26, wherein thecritical dimension is about 30 nm or less
 28. The partially fabricatedintegrated circuit of claim 27, wherein the critical dimension is about20 nm or less.
 29. The partially fabricated integrated circuit of claim25, wherein the block moieties include polymethylmethacrylate.
 30. Thepartially fabricated integrated circuit of claim 25, wherein the blockmoieties include polystyrene.
 31. The partially fabricated integratedcircuit of claim 22, wherein the guides comprise silicon.
 32. Thepartially fabricated integrated circuit of claim 31, wherein the guidescomprise silicon oxide.